J. Chem.

Thermodynamics 40 (2008) 12481252

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Selection of ionic liquids as entrainers for separation of (water + ethanol)

Yun Ge, Lianzhong Zhang *, Xingcai Yuan, Wei Geng, Jianbing Ji
College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310014, China

a r t i c l e i n f o a b s t r a c t

Article history: For selection of ionic liquids (ILs) which can be potentially used as entrainers for separation of the azeotro-
Received 30 January 2008 pic mixture of (water + ethanol) by extractive distillation, (vapor + liquid) equilibrium was measured for
Received in revised form 25 March 2008 the ternary systems of (water + ethanol + an IL) using a previously proposed ebulliometer. The experimen-
Accepted 29 March 2008
tal measurement was performed at p = 100 kPa and in a way of continuous synthesis, in which analysis of
Available online 7 April 2008
liquid phase composition was avoided. While the mole fraction of ethanol calculated on IL-free basis, x02 ,
was kept almost unchanged at 0.95, isobaric T, x, y data were measured at different IL mass fractions. Activ-
Keywords:
ity coefcients, as well as relative volatilities, of the volatile components were obtained from the experi-
Ionic liquid
Entrainer
mental data without the need of a thermodynamic model of the liquid phase. There were eight ILs in our
Ethanol investigation: 1-butyl-3-methylimidazolium tetrauoroborate ([bmim][BF4]), 1-ethyl-3-methylimidazo-
Activity coefcient lium tetrauoroborate ([emim][BF4]), 1-butyl-3-methylimidazolium dicyanamide ([bmim][N(CN)2]),
Relative volatility 1-ethyl-3-methylimidazolium dicyanamide ([emim][N(CN)2]), 1-butyl-3-methylimidazolium chloride
([bmim][Cl]), 1-ethyl-3-methylimidazolium chloride ([emim][Cl]), 1-butyl-3-methylimidazolium acetate
([bmim][OAc]), and 1-ethyl-3-methylimidazolium acetate ([emim][OAc]). The effect of the ILs on the rel-
ative volatility of the volatile components was depicted separately by their effect on the activity coef-
cients. The results indicated that, among the eight ILs studied, [emim][Cl] has the largest effect on
enhancement of the relative volatility. Another IL, [emim][OAc], has also signicant effect. Considering
the relatively low viscosity and melting point of [emim][OAc], this IL might be favorable candidate as
entrainer for potential industrial application.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, ionic liquids (ILs) have attracted considerable
attention for their potential use as entrainers for separation of aze-
otropic or close boiling mixtures [13]. In our previous work [46],
we presented an ebulliometer for measurement of T, x, y data at
constant pressure by continuous synthesis. The design of the ebull-
iometer ensured reliability of the vapor-phase composition when
the amount of vapor hold-up and vapor circulation were relatively
small. A procedure was presented for the calculation of liquid
phase composition. The tedious procedure for liquid phase analysis
was avoided. For selection of ILs which can be potentially used for
the separation of the azeotropic mixture of (water + 2-propanol) by
extractive distillation, (vapor + liquid) equilibrium (VLE) was mea-
sured for the ternary systems of (water + 2-propanol + IL) at
p = 100 kPa [6]. While the mole fraction of 2-propanol calculated
on IL-free basis, x02 , was kept almost unchanged at 0.95, isobaric
T, x, y data were measured at different IL mass fractions. The mea-
surements provided directly the dependence of the relative volatil-
ity on the IL mass fraction. Activity coefcients of the volatile
components were obtained without the need of a thermodynamic
* Corresponding author. Tel.: +86 571 88320892.
E-mail address: zhanglz@zjut.edu.cn (L. Zhang).
model of the liquid phase. Effect of the ILs on the relative volatility
was also depicted by their effect on the activity coefcients.
In this work, experimental evaluation of ILs as entrainers was pre-
sented for the azeotropic mixture of (water + ethanol). Separation of
this mixture is often required in industry. The ILs studied are system-
atically composed of an anion chosen from [BF4], [N(CN)2], [Cl],
or [OAc], and a cation from [bmim]+ or [emim]+. Therefore their
were eight ILs in this work: 1-butyl-3-methylimidazolium tetrauo-
roborate ([bmim][BF4]), 1-ethyl-3-methylimidazolium tetrauoro-
borate ([emim][BF4]), 1-butyl-3-methylimidazolium dicyanamide
([bmim][N(CN)2]), 1-ethyl-3-methylimidazolium dicyanamide
([emim][N(CN)2]), 1-butyl-3-methylimidazolium chloride ([bmim]
[Cl]), 1-ethyl-3-methylimidazolium chloride ([emim][Cl]), 1-butyl-
3-methylimidazolium acetate ([bmim][OAc]), and 1-ethyl-3-meth-
ylimidazolium acetate ([emim][OAc]).
Several authors have reported ternary VLE data for systems con-
taining water, ethanol, and an IL. The ILs that have been studied in-
clude: [bmim][BF4], [emim][BF4], and [bmim][Cl] by Jork et al. [7];
1,3-dimethylimidazolium dimethylphosphate ([mmim][DMP]),
1-ethyl-3-methylimidazolium diethylphosphate ([emim][DEP]),
1-butyl-3-methylimidazolium bromide ([bmim][Br]), 1-butyl-3-
methylimidazolium chloride ([bmim][Cl]) and 1-butyl-3-methyl-
imidazolium hexauorophosphate ([bmim][PF6]) by Zhao et al.
[8,9]; 1,3-diethylimidazolium diethylphosphate([eeim][DEP]) by

0021-9614/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2008.03.016
 Y. Ge et al. / J. Chem. Thermodynamics 40 (2008) 12481252 1249

Jiang et al. [10]; 1-ethyl-3-methylimidazolium dimethylphosphate TABLE 1

([emim][DMP]) and 1-ethyl-3-methylimidazolium ethyl sulfate (Vapor + liquid) equilibrium data for the systems {water (1) + ethanol (2) + IL (3)} at
p = 100 kPa
([emim][ES]) by Wang et al. [11,12]; [bmim][Cl] and 1-hexyl-3-
methylimidazolium chloride ([hmim][Cl]) by Calvar et al. [13,14]. x02 a w3a y2 T/K c1 c2 a21b
ILs with an anion of [N(CN)2] or [OAc] have not been studied for IL = [bmim][BF4]
separation of the azeotropic mixture of (water + ethanol). These ILs 0.9502 0.9084 0.9818 372.15 1.10 1.40 2.83
have relatively low melting point and viscosity. The aims of the pres- 0.9501 0.8000 0.9780 360.01 1.27 1.31 2.34
0.9501 0.7000 0.9745 356.15 1.39 1.23 2.01
ent work are to illustrate the performance of the ILs in enhancement 0.9501 0.6000 0.9701 354.65 1.54 1.15 1.70
of the relative volatility of the azeotropic mixture, to relate the ef- 0.9501 0.4999 0.9663 353.49 1.68 1.11 1.51
fects of the ILs on the relative volatility with their effects on the activ- 0.9500 0.3999 0.9629 352.87 1.79 1.07 1.37
ity coefcients, and to relate the performance of the ILs with their 0.9500 0.3001 0.9596 352.35 1.91 1.04 1.25
0.9500 0.2000 0.9552 351.91 2.08 1.02 1.12
structure. These are important for the potential application of the ILs.
0.9499 0.1000 0.9518 351.45 2.22 1.01 1.04
IL = [emim][BF4]
2. Experimental 0.9499 0.9001 0.9883 365.61 0.92 1.82 4.46
0.9501 0.8001 0.9848 356.84 1.05 1.58 3.42
0.9501 0.7000 0.9808 354.00 1.20 1.40 2.68
2.1. Materials
0.9501 0.5999 0.9765 353.00 1.34 1.27 2.18
0.9501 0.5000 0.9720 352.60 1.48 1.18 1.83
Water was double distilled. Ethanol was analytical grade re- 0.9501 0.4000 0.9680 352.50 1.60 1.11 1.59
agent and was used without further purication. Purity of ethanol 0.9501 0.3000 0.9630 352.13 1.79 1.07 1.37
was checked by g.c. and the result was 99.9%, while KarlFischer 0.9500 0.2001 0.9585 351.79 1.96 1.04 1.21
0.9500 0.0999 0.9539 351.47 2.14 1.01 1.09
analysis indicated 5.2  104 water content. The ILs [bmim][Cl],
[emim][Cl], [bmim][BF4], [emim][BF4], [bmim][N(CN)2], [emim] IL = [bmim][N(CN)2]
0.9501 0.7996 0.9802 373.95 0.67 0.82 2.71
[N(CN)2], were prepared using published methods in the literature
0.9500 0.7000 0.9776 365.25 0.89 0.91 2.29
[15]. [bmim][Cl] was synthesized by reaction of 1-methylimidazole 0.9500 0.5999 0.9748 360.00 1.10 0.96 1.98
and 1-chlorobutane under a nitrogen atmosphere. [emim][Cl] was 0.9500 0.5000 0.9709 356.85 1.31 0.99 1.73
synthesized by reaction of 1-methylimidazole and chloroethane in 0.9500 0.3999 0.9671 354.82 1.52 1.00 1.51
0.9499 0.3001 0.9633 353.41 1.74 1.01 1.33
a pressure vessel. The products were further puried by recrystal-
0.9499 0.2000 0.9598 352.40 1.94 1.01 1.19
lization in ethyl acetate/acetonitrile solvent. Consequently, 0.9499 0.1000 0.9550 351.70 2.16 1.00 1.07
[bmim][BF4], [emim][BF4], [bmim][N(CN)2], and [emim][N(CN)2]
IL = [emim][N(CN)2]
were prepared by a procedure of anion metathsis, which has been 0.9500 0.7998 0.9857 374.41 0.54 0.88 3.62
described in our previous work [4,6]. [emim][OAc] and [bmim] 0.9501 0.7001 0.9820 365.92 0.74 0.94 2.86
[OAc] were prepared by a patented anion metathesis procedure, 0.9501 0.6000 0.9778 361.09 0.95 0.97 2.31
in which ethanol is used as solvent and potassium acetate is used 0.9501 0.5000 0.9729 357.65 1.20 0.99 1.88
0.9501 0.3999 0.9694 355.44 1.38 1.00 1.66
as the source of anion [16]. Before use, all ILs were dried for 24 h
0.9501 0.3000 0.9628 353.83 1.70 1.01 1.36
under vacuum at 340 K to remove volatile impurities. 0.9500 0.1999 0.9576 352.58 1.95 1.01 1.19
0.9500 0.1000 0.9535 351.64 2.14 1.01 1.08

2.2. Experimental apparatus IL = [bmim][OAc]

0.9501 0.5998 0.9740 377.15 0.60 0.53 1.96
0.9500 0.5000 0.9718 367.48 0.84 0.68 1.81
VLE were measured at p = 100 kPa and by an ebulliometer made
0.9500 0.4000 0.9691 360.87 1.11 0.81 1.65
of quartz glass. Detailed description of the ebulliometer is available 0.9500 0.3000 0.9652 356.73 1.39 0.89 1.46
in the previous work [6]. A 20 dm3 glass container was used as 0.9500 0.2000 0.9609 353.72 1.70 0.96 1.29
pressure buffer. The pressure measurement was by a U-tube lled 0.9499 0.0999 0.9550 351.87 2.05 1.00 1.12
with water, one end connected to the pressure buffer and another IL = [emim][OAc]
to the atmosphere. Atmospheric pressure was measured using a 0.9500 0.6003 0.9809 380.12 0.41 0.50 2.69
0.9500 0.5002 0.9771 369.43 0.66 0.65 2.24
standard barometer. Uncertainty of the pressure measurement
0.9500 0.4001 0.9729 361.94 0.96 0.79 1.88
was 0.05 kPa. Temperature measurement was by a standard plat- 0.9500 0.3000 0.9687 356.85 1.28 0.91 1.62
inum thermometer (Taihe Instrument Co.) and a 6-1/2-digit mul- 0.9500 0.2000 0.9636 353.76 1.60 0.97 1.39
timeter (Kethley Model 2000). Uncertainty of the resistance 0.9500 0.0999 0.9567 351.99 1.98 1.00 1.16
measurement was 8 mX, which is equivalent to 0.08 K for tem- IL = [bmim][Cl]
perature measurement. 0.9500 0.5881 0.9769 371.16 0.67 0.67 2.22
0.9500 0.4999 0.9728 364.43 0.93 0.77 1.87
0.9500 0.3999 0.9683 358.90 1.25 0.88 1.60
2.3. Experimental procedure 0.9500 0.3009 0.9640 355.37 1.55 0.95 1.40
0.9500 0.2000 0.9595 353.21 1.82 0.99 1.24
VLE measurement was carried out in a way of continuous syn- 0.9500 0.1000 0.9538 351.89 2.12 1.00 1.08

thesis. The mole fraction of ethanol calculated on IL-free basis, x02 , IL = [emim][Cl]
was kept almost unchanged at 0.95. At the beginning of the mea- 0.9500 0.5906 0.9848 373.52 0.43 0.65 3.40
0.9500 0.5001 0.9803 366.38 0.65 0.76 2.62
surement, certain amount of water, ethanol, and an IL were intro-
0.9501 0.3997 0.9748 360.25 0.97 0.87 2.04
duced into the ebulliometer to form the rst synthesis. Water 0.9501 0.3000 0.9696 356.26 1.28 0.94 1.67
contents of ethanol and the ILs were determined by KarlFischer 0.9501 0.2001 0.9634 353.68 1.63 0.98 1.38
analysis. Every sample added in or taken out of the ebulliometer 0.9501 0.1000 0.9561 352.06 2.01 1.00 1.14
was weighed by an electronic balance (Mettler-Toledo AL204) with a
Compositions reported are of equilibrium liquid.
an uncertainty of 0.0002 g. When equilibrium was established, b
a21 y2 =x02 =y1 =x01 .
vapor condensate was sampled and analyzed. As the ILs are non-
volatile, the vapor phase is composed of water and ethanol. content using the KarlFischer method, with an uncertainty of
Vapor-phase composition was determined by analyzing the water 0.0001 in water mole fraction or relatively 0.5%, whichever is the
1250 Y. Ge et al. / J. Chem. Thermodynamics 40 (2008) 12481252

greater. The density of the vapor condensate was calculated based
on correlation of the literature data at 298.15 K for (water + etha-
nol) [17]. Amount of (water + ethanol) existing as vapor material
was calculated from the composition, density, and volume of the
vapor material. In this work, the volume of vapor material, V,
was estimated to be 1.7 cm3. Other than the vapor material, the
remaining material in the ebulliometer was regarded as bulk mate-
rial. Quantity of every component in the bulk material was calcu-
lated according to material balance, and the bulk compositions
were obtained. Consequently, the liquid phase compositions were
calculated on the basis of vapor to liquid circulation ratio, which
is expressed in mass quantities, bm. Detailed description and for-
mulation of the calculation procedure is available in our previous
work [4,6]. The synthesis for the next point of measurement was
carried out by replacement of certain amount of bulk material with
IL-free mixture of (water + ethanol) to keep x02 almost unchanged at
0.95. The measurement was repeated until w3 became close to 0.1.
In our measurement, vapor phase circulation was maintained at
1 cm3  min1 by adjustment of the heating power. Liquid phase
circulation was enhanced by use of the pump-like stirrer and
was set at approximately 200 cm3  min1. Neglecting the inuence
of density, bm had a value of 0.005.
in which N is the number of data points. Results for the optimized
parameters and deviations in the correlations are summarized in
table 2.
The effect of the ILs on the relative volatility and its concentra-
tion dependence are shown in gure 1. The relative volatilities, a21,
are for the ternary system of {water (1) + ethanol (2) + IL (3)} at
x02 0:95 and p = 100 kPa. When there is no IL added, a21 = 0.9,
indicating the existing of an azeotrope. All of the eight ILs can en-
hance the relative volatility and break the azeotrope. The mini-
mum values of w3 required to break the azeotrope were given in
table 3. These values were calculated at the limit condition of
x01 0 using correlation parameters in table 2. It can be observed
4.5
4.0
3.5
3.0

21
3. Results and discussion
2.5
The experimental isobaric VLE data for IL-containing ternary
system at p = 100 kPa are listed in table 1. For the system {water 2.0
(1) + ethanol (2) + IL (3)}, data were measured at different IL mass
fractions, w3, and at x02 0:95. The liquid phase compositions were 1.5
reported in x02 and w3. Activity coefcients of the volatile compo-
nents were also reported. In the calculation of the activity coef-
1.0
cients, the vapor phase was regarded as ideal gas and the vapor 0.0 0.2 0.4 0.6 0.8 1.0
pressures were calculated by parameters in the literature [18]. w3
In the measurements, temperature stability was better than
0.02 K. As discussed in our previous work [6], the uncertainties FIGURE 1. Relative volatility a21 for the quasi-binary system {water (1) + ethanol
for the reported w3 and x02 were estimated to be 0.003 and (2)} enhanced by addition of an IL (3) at p = 100 kPa and x02 0:95: , [bmim][BF4];
0.0005, respectively. }, [emim][BF4]; N, [bmim][N(CN)2]; M, [emim][N(CN)2]; d, [bmim][OAc]; , 
[emim][OAc]; j, [bmim][Cl]; h, [emim][Cl]. Lines were calculated by NRTL at
The experimental VLE data were correlated with the NRTL equa- x02 0:95 using correlation parameters in table 2.
tion [19]. In the correlations, the binary parameters for
(water + ethanol) were taken from the literature [20]. For the sim-
plicity of application, the values of a13 and a23 were set as 0.3. The TABLE 3
remaining four binary parameters were tted by optimization of Minimum value of mass fraction of IL, w3, which is needed to break the water +
the following objective function: ethanol azeotrope
v
u N Cation w3a required for ILs having different cations and anions
uX
F t T =K  T =K2 =N  4
cal exp
[Cl] [OAc] [N(CN)2] [BF4]
n1
v [emim]+ 0.050 0.048 0.076 0.080
u N
uX [bmim]+ 0.072 0.056 0.088 0.114
100t y2;cal  y2;exp 2 =N  4 1
a
n1 Calculated at the limit condition of x01 0 using correlation parameters in table 2.

TABLE 2
NRTL parameters, Dg, obtained from correlations of experimental VLE data and standard deviations, rT and ry, for the systems {water (1) + ethanol (2) + IL (3)} at p = 100 kPa

IL Optimized binary parametersa Standard deviations

Dg13/(J  mol1) Dg31/(J  mol1) Dg23/(J  mol1) Dg32/(J  mol1) rT/Kb r yc
[bmim] [BF4] 5406.9 3523.1 8301.9 2799.6 0.14 0.0004
[emim] [BF4] 5410.1 4061.1 9092.0 1624.6 0.18 0.0005
[bmim] [N(CN)2] 3918.9 6671.9 1987.8 1015.9 0.11 0.0005
[emim] [N(CN)2] 2410.5 1854.0 2911.0 3453.5 0.08 0.0007
[bmim][OAc] 4388.3 9418.4 5192.2 9001.1 0.15 0.0003
[emim][OAc] 14357 8789.9 12775 8266.2 0.32 0.0007
[bmim][Cl] 10193 6060.7 8008.0 6185.7 0.23 0.0005
[emim][Cl] 7542.2 5655.1 3035.2 6174.8 0.25 0.0004
a
Binary parameters for water and ethanol were xed as Dg12/(J  mol1) = 3698.8 + 4.2758(T/K), Dg21/(J  mol1) = 2216.0 + 6.7055(T/K), and a12 = 0.4, which were taken
from the literature [20]. The values for a13 and a23 were set as 0.3. Objective function used in the optimization was shown in Eq. (1).
q
P
b
rT =K T cal =K  T exp =K2 =N  4.
qP
c
ry y2;cal  y2;exp 2 =N  4.
 Y. Ge et al. / J. Chem. Thermodynamics 40 (2008) 12481252
2.4
2.0
1.6
1
1.2
0.8
0.4
0.0 0.2 0.4 0.6
w3
FIGURE 2. Activity coefcients of water, c1, and ethanol, c2, in the saturated liquid mixtures {water (1) + ethanol (2) + IL (3)} at p = 100 kPa and x02 0:95: , [bmim][BF4]; e,
 
[emim][BF4]; N, [bmim][N(CN)2]; M, [emim][N(CN)2]; , [bmim][OAc]; , [emim][OAc]; j, [bmim][Cl]; h, [emim][Cl]. Lines were calculated by NRTL at x02 0:95 using
correlation parameters in table 2.
that the amount of IL required for breaking the azeotrope of
(water + ethanol) is much less than that for (water + 2-propanol)
[6]. When [emim][Cl] or [emim][OAc] is used, the minimum w3 re-
quired is approximately 0.05. Therefore, these two ILs are good
candidates to be used as entrainers for separating water and etha-
nol. The IL, [emim][OAc], has also much lower viscosity and melt-
ing point than [emim][Cl], therefore it might be more favorable for
potential industrial application. When w3 increases, a21 becomes
larger. As shown in gure 1, the effect of the ILs depends on both
the anion and the cation. For ILs having the same anion and differ-
ent cations, the effect is in the order of [emim]+ > [bmim]+. On the
other hand, for ILs having the same cation and different anions, the
effect has relatively complicated concentration dependence. When
relatively small amount of ILs is used, namely w3 < 0.2, the IL with
the anion of [OAc] ([bmim][OAc] or [emim][OAc]) has the most
signicant effect among ILs with the same cation. However, effect
of these two ILs increases relatively slowly when w3 becomes lar-
ger. For ILs with the other three anions, the effect is in the order of
[Cl] > [N(CN)2] > [BF4]. The signicant effect of ILs with [Cl]
has also been illustrated in the literature [7,8].
The relative volatility a21 is related with the activity coefcients
by a21 c2 =c1  psat sat sat sat
2 =p1 , in which the ratio p2 =p1 is a natural
contribution to a21. It is insensitive to temperature and keeps effec-
tively unchanged at 2.242.29 in the present measurement. There-
fore, the effect of ILs on a21 can be separately depicted by their
effect on c1 and c2. Because the ILs under investigation are com-
posed of a pair of cation and anion out of four different anions
and two different cations, the effect of the ILs also reect the effect
of anions and cations. The activity coefcients of water and ethanol
and their dependence on IL mass fraction, w3, are shown in gure 2.
The activity coefcients are related with the condition of saturated
liquid at p = 100 kPa and x02 0:95. It can be observed that the an-
ion has much more inuence on the activity coefcients than cat-
ion. The activity coefcient of water, c1, shows signicantly
different values for different anions and the values decrease in an
order of [OAc]  [Cl] < [N(CN)2] < [BF4], indicating that the
interactions of the anions with water are in the order of
[OAc]  [Cl] > [N(CN)2] > [BF4]. At the same time the anions
have even more signicant effect on c2. With the increase of w3,
c2 increases for ILs with [BF4], decreases slowly for IL with
[N(CN)2], and decreases rapidly for ILs with [Cl] and [OAc].
1251
1.8
1.6
1.4
1.2
2
1.0
0.8
0.6
0.4
0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
w3
Therefore, the interactions of the anions with ethanol are in the
similar order, namely [OAc] > [Cl] > [N(CN)2]> [BF4]. The simi-
larity in the interactions cancels the effect of ILs in some extent and
accounts for the result that we do not observe dramatic increase of
the relative volatility by addition of the ILs. Also the strong interac-
tion between [OAc] and ethanol is responsible for the relatively
slow increase of a21 at large IL concentrations. On the other hand,
the cations have also important inuence on the activity coef-
cients. For ILs with [N(CN)2] and [BF4], the effects of cations
show reversed order for c1 and c2. The values of c1 are in the order
[emim]+ < [bmim]+, while the values of c2 are in the order
[emim]+ > [bmim]+. The reversed effect on the activity coefcients
results in a consistent effect on the relative volatility. For ILs with
[OAc] and [Cl], the difference in cation has little effect on c2,
while having signicant inuence on c1. The values of c1 are in
the orders [emim]+ < [bmim]+. The relatively strong effect of
[emim]+ on c1, together with the relatively small effect of [Cl]
(as compared with [OAc]) on c2, illustrates the reason why
[emim][Cl], among the eight ILs studied, has the largest effect on
enhancement of the relative volatility.
Lines in gure 2 were calculated by NRTL at x02 0:95 using cor-
relation parameters in table 2. The NRTL model provided good cor-
relation for the activity coefcients, at least at the experimental
conditions with small water content.
4. Conclusions
Isobaric T, x, y data were measured for ternary systems contain-
ing (water + ethanol + an IL) at p = 100 kPa. At a xed ethanol-to-
water ratio, namely x02 0:95, measurements were performed in
a way of continuous synthesis at various IL concentrations. The
measurements provided directly the dependence of the relative
volatility on the IL mass fraction. Activity coefcients of the volatile
components were obtained without the need of a thermodynamic
model of the liquid phase. Eight ILs, composed of an anion chosen
from [BF4], [N(CN)2], [Cl], or [OAc], and a cation from [bmim]+
or [emim]+, were studied. The effect of IL on relative volatility was
separately depicted by effect of anion and cation on the activity
coefcient of water and ethanol, respectively. The results indicated
that, among the eight ILs studied, [emim][Cl] has the largest effect
on enhancement of the relative volatility. Another IL, [emim][OAc],
1252 Y. Ge et al. / J. Chem. Thermodynamics 40 (2008) 12481252
has also signicant effect. Considering the relatively low viscosity
and melting point of [emim][OAc], it might be favorable candidate
as entrainer for potential industrial application.
Acknowledgements
This work is nancially supported by the National Natural
Science Foundation of China (20776132) and the Science Founda-
tion of Zhejiang Province (Z405507).
References
[1] W. Arlt, M. Seiler, C. Jork, T. Schneider, German Patent DE 10114734, 2001.
[2] J. Gmehling, M. Krummen, German Patent DE 10154052, 2003.
[3] K.N. Marsh, J.A. Boxall, R. Lichtenthaler, Fluid Phase Equilibr. 219 (2004) 9398.
[4] L. Zhang, D. Deng, J. Han, D. Ji, J. Ji, J. Chem. Eng. Data 52 (2007) 199205.
[5] L. Zhang, J. Han, R. Wang, X. Qiu, J. Ji, J. Chem. Eng. Data 52 (2007) 14011407.
[6] L. Zhang, J. Han, D. Deng, J. Ji, Fluid Phase Equilibr. 255 (2007) 179185.
[7] C. Jork, M. Seiler, W. Arlt, J. Chem. Eng. Data 49 (2003) 852857.
[8] J. Zhao, C. Dong, C. Li, H. Meng, Z. Wang, Fluid Phase Equilibr. 242 (2006) 147
153.
[9] J. Zhao, C. Li, Z. Wang, J. Chem. Eng. Data 51 (2006) 17551760.
[10] X. Jiang, J. Wang, C. Li, L. Wang, Z. Wang, J. Chem. Thermodynamics. 39 (2007)
841846.
[11] J. Wang, C. Li, Z. Wang, Z. Li, Y. Jiang, Fluid Phase Equilibr. 255 (2007)
186192.
[12] J. Wang, C. Li, Z. Wang, J. Chem. Eng. Data 52 (2007) 13071312.
[13] N. Calvar, B. Gonzalez, E. Gomez, A. Dominguez, J. Chem. Eng. Data 51 (2006)
21782181.
[14] N. Calvar, B. Gonzalez, E. Gomez, A. Dominguez, Fluid Phase Equilibr. 259
(2007) 5156.
[15] C. Gordon, in: P. Wasserscheid, T. Welton (Eds.), Ionic Liquids in Synthesis,
WileyVCH, Weiheim, 2002, pp. 721.
[16] L. Zhang, J. Ji, D. Deng, Z. Shu, X. Chen, Chinese Patent Application, CN
101108827A.
[17] J. Herraez, R. Belda, J. Solution. Chem. 35 (2006) 13151328.
[18] R. Reid, J. Prausnitz, B. Poling, The Properties of Gases and Liquids, McGraw-
Hill, New York, 1987 (Appendix A).
[19] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135144.
[20] Y. Tang, H. Huang, I. Chien, J Chem. Eng. Jpn. 36 (2003) 13521363.
JCT 08-49